JP4543171B2 - Iron alloy for high resistors - Google Patents
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本発明は、優れた加工性を有し、高い比抵抗(μΩ・ｃｍ)と小さい抵抗値温度係数(ｐｐｍ／℃)とを兼ね備えた、抵抗器として用いるのに好適な鉄合金に関するものである。 The present invention relates to an iron alloy suitable for use as a resistor, having excellent workability and having a high specific resistance (μΩ · cm) and a small resistance value temperature coefficient (ppm / ° C.). .
現在では高抵抗器用のエレメントの線材として、Ｎｉ−Ｃｒ−Ａｌ−Ｓｉ、Ｎｉ−Ｃｒ合金などが使用されている。特に高抵抗器線材には、（１）温度による影響が小さいこと（熱による抵抗値変化が小さい→低温度係数）、（２）比抵抗が大きいこと、（３）抵抗値の経時変化が小さいこと、（４）加工性に富むこと、（５）半田付けやスポット溶接性がよいこと、（６）耐腐食性、（７）対熱応力断線性などの性能が要求される。最近では、抵抗器の信頼性の向上、巻き線作業性の向上のためにさらなる比抵抗値の増加が求められている。 At present, Ni—Cr—Al—Si, Ni—Cr alloys, and the like are used as wire rods for elements for high resistors. Especially for high-resistor wires, (1) the effect of temperature is small (resistance change due to heat is small → low temperature coefficient), (2) the specific resistance is large, and (3) the resistance value changes with time is small. In addition, (4) high workability, (5) good soldering and spot weldability, (6) corrosion resistance, (7) resistance to thermal stress disconnection, etc. are required. Recently, there has been a demand for further increase in specific resistance value in order to improve the reliability of the resistor and to improve the winding workability.
近年、計測器、精密電源、電気自動車などの高性能化・発展に伴い、精密抵抗材料、特に高い比抵抗値・優れた温度特性を有する抵抗材料の開発が望まれている。従来、精密抵抗材料としてＣｕ−Ｍｎ合金、Ｎｉ−Ｃｕ合金、Ｎｉ−Ｃｒ系合金などが使用されている。Ｃｕ−Ｍｎ合金やＮｉ−Ｃｕ合金は温度特性に優れているものの、比抵抗値が小さく高抵抗器用材料としての使用は不可とされている。一方、Ｎｉ−Ｃｒ系合金は、比抵抗値が高いため高抵抗材料へ適用されているが、比抵抗値の大きさが未だ不十分であり、例えば、計測器、電気自動車などに使用される巻線型抵抗器に使用する場合、抵抗を大きくするために線径を非常に細くしなければならず(φ０．０２ｍｍ程度)、巻き作業中に断線してしまうという問題があった。 In recent years, with the improvement and development of measuring instruments, precision power supplies, electric vehicles, etc., development of precision resistance materials, particularly resistance materials having high specific resistance values and excellent temperature characteristics, is desired. Conventionally, Cu—Mn alloys, Ni—Cu alloys, Ni—Cr alloys and the like have been used as precision resistance materials. Although Cu-Mn alloy and Ni-Cu alloy are excellent in temperature characteristics, their specific resistance values are small and their use as high-resistor materials is not possible. On the other hand, Ni—Cr-based alloys are applied to high-resistance materials because of their high specific resistance values, but the specific resistance values are still insufficient, and are used, for example, in measuring instruments and electric vehicles. When used in a wire-wound resistor, the wire diameter has to be made very thin (about φ0.02 mm) in order to increase the resistance, and there is a problem that the wire breaks during the winding operation.
本発明に関連する高い比抵抗(μΩ・ｃｍ)と小さい抵抗値温度係数(ｐｐｍ／℃)とを兼ね備えた、抵抗器として用いるのに好適な鉄合金に関する合金としては、１０〜２６重量％クロム、３．５〜１５重量％銅および２．５〜１０％アルミニウムの合計２５〜４０％、０．０１〜２０重量％コバルト、０．０１〜５重量％マンガン、０．０１〜５重量％タングステン、０．０１〜５重量％チタンおよび０．０１〜５重量％シリコンの内から選ばれた１種あるいは２種以上の合計０．０１〜２０重量％および残部ニッケルからなる精密抵抗合金がある。（例えば特許文献１参照）しかしながら、特許文献１に記載の合金は、４０重量％以上のニッケルからなる合金であり、複雑な加工工程を得て成形される。また、比抵抗値も１５０μΩ・ｃｍ以下であり、未だ十分とは言えない。
本発明は、加工性に優れ、高い比抵抗値および低い抵抗値温度係数を兼ね備え、耐熱性、耐食性にも優れた材料を提供することを課題とする。 An object of the present invention is to provide a material having excellent workability, a high specific resistance value, a low resistance temperature coefficient, and excellent heat resistance and corrosion resistance.
本発明によれば、Ｍｎ：１０．０〜４５．０重量％、Ａｌ：５．０〜１５．０重量％、Ｃ：０．０１〜２．０重量％、Ｃｒ：０．０１〜１５．０重量％、残部Ｆｅ及び不可避的不純物からなることを特徴とする高抵抗器用鉄合金が得られる。 According to the present invention, Mn: 10.0-45.0 wt%, Al: 5.0-15.0 wt%, C: 0.01-2.0 wt%, Cr: 0.01-15. An iron alloy for high resistors, characterized by comprising 0% by weight, the balance Fe and unavoidable impurities, is obtained.
また本発明によれば、１５０（μΩ・ｃｍ）以上の比抵抗値を有する高抵抗器用鉄合金が得られる。 Moreover, according to the present invention, an iron alloy for high resistors having a specific resistance value of 150 (μΩ · cm) or more can be obtained.
また本発明によれば、抵抗値の温度係数が±２００ｐｐｍ／℃の範囲内である高抵抗器用鉄合金が得られる。 Moreover, according to this invention, the iron alloy for high resistors whose temperature coefficient of resistance value is in the range of +/- 200 ppm / degrees C is obtained.
また本発明によれば、時効熱処理により抵抗値の温度係数を低く制御した高抵抗器用鉄合金が得られる。 Moreover, according to this invention, the iron alloy for high resistors which controlled the temperature coefficient of resistance value low by aging heat processing is obtained.
また本発明によれば、添加元素として、さらにＢ：０．００１〜１．５重量％、Ｎ：０．００１〜１．５重量％、Ｂｅ、Ｍｇ、Ｓｉ、Ｔｉ、Ｖ、Ｃｏ、Ｎｉ、Ｃｕ、Ｎｂ、Ｍｏ及びＷ：それぞれ０．０１〜５．０重量％、からなる群から選択した１種又は２種以上の元素を含有することを特徴とする高抵抗器用鉄合金が得られる。Further, according to the present invention, as additional elements, B: 0.001 to 1.5% by weight, N: 0.001 to 1.5% by weight, Be, Mg, Si, Ti, V, Co, Ni, Cu, Nb, Mo and W: each 0.01 to 5.0 wt%, the high-resistance dexterity iron alloy, characterized in that it comprises containing one or more elements selected from the group consisting of is obtained.
組成範囲について、Ｍｎ：１０．０〜４５．０重量％とする理由は、５．０重量％未満では、高い比抵抗値を実現できず、４５．０重量％以上であると、耐食性が劣化するからである。特にＭｎ：１５．０〜４０．０重量％が望ましい。これにより高い比抵抗値および耐食性に富む材料を実現することができる。 The reason why the composition range is Mn: 10.0 to 45.0% by weight is that if it is less than 5.0% by weight, a high specific resistance value cannot be realized, and if it is 45.0% by weight or more, the corrosion resistance deteriorates. Because it does. In particular, Mn: 15.0 to 40.0% by weight is desirable. As a result, a material having a high specific resistance value and high corrosion resistance can be realized.
Ａｌについては、５．０〜１５．０重量％とする利用は、５．０重量％未満では高抵抗値が得られず、１５．０重量％を超えると、十分な加工性が得られないからである。特に、Ａｌ:７．０〜１４．０重量％が望ましい。これにより高い比抵抗値と十分な加工性を得ることができる。また、Ｃについては、０．０１〜２．０重量％とする理由は、０．０１重量％以下では、小さい抵抗値温度係数を得ることができず、２．０重量％を超えると多量のＦｅ３ＣやＭｎ３Ｃなどの炭化物の析出により脆くなり、また耐熱性が劣化するからである。更に、Ｃｒについては、０．０１〜１５．０重量％とする理由は、０．０１重量％以下では、十分な耐食性を得ることができず、１０．０重量％を超えると、σ相などの金属間化合物の析出により十分な加工性が得られないからである。 For Al, the use of 5.0 to 15.0% by weight is not possible to obtain a high resistance value if it is less than 5.0% by weight, and sufficient workability cannot be obtained if it exceeds 15.0% by weight. Because. In particular, Al: 7.0 to 14.0% by weight is desirable. Thereby, a high specific resistance value and sufficient workability can be obtained. Moreover, about C, the reason for setting it as 0.01 to 2.0 weight% is that if it is 0.01 weight% or less, a small resistance temperature coefficient cannot be obtained, and if it exceeds 2.0 weight%, a large amount It is because it becomes brittle by precipitation of carbides such as Fe 3 C and Mn 3 C, and heat resistance deteriorates. Furthermore, with respect to Cr, the reason for 0.01 to 15.0% by weight is that if it is 0.01% by weight or less, sufficient corrosion resistance cannot be obtained. This is because sufficient workability cannot be obtained by precipitation of the intermetallic compound.
本発明の高抵抗器用鉄合金は、必要に応じて、さらにＢ：０．００１〜１．５重量％、Ｎ：０．００１〜１．５重量％、Ｂｅ、Ｍｇ、Ｓｉ、Ｔｉ、Ｖ、Ｃｏ、Ｎｉ、Ｃｕ、Ｎｂ、Ｍｏ及びＷ：それぞれ０．０１〜５．０重量％、からなる群から選択した１種又は２種以上の元素を含有させることができる。その添加効果を高めるための、成分の数値限定の理由は、次の通りである。The iron alloy for high resistors of the present invention may further include B: 0.001 to 1.5% by weight, N: 0.001 to 1.5% by weight, Be, Mg, Si, Ti, V, if necessary. Co, Ni, Cu, Nb, Mo and W: each 0.01 to 5.0 wt%, one or more elements selected from the group consisting of can be free Yes. The reason for limiting the numerical values of the components to enhance the effect of the addition is as follows.
Ｂについては、０．００１〜１．５重量％とする理由は、０．００１重量％未満では鋳造組織及び鍛造組織においても微細な結晶粒組織を得るための添加効果が小さく、また１．５重量％を超えると硼素化合物等の析出により脆化してしまうからである。また、Ｎについては、０．００１〜１．５重量％とする理由は、０．００１重量％未満では十分な加工性を得るための添加効果が小さく、１．５重量％を超えると窒化物等の析出により脆化するからである。更に、Ｂｅ、Ｍｇ、Ｓｉ添加については、材料強化に有効であり、Ｔｉ添加は粒界腐食の防止に有効であり、Ｖ添加は耐摩耗性改善に有効であり、Ｃｏ又はＮｉ添加はγ相の安定化による加工性改善に有効であり、Ｃｕ又はＮｂ添加は耐食性改善に有効であり、Ｍｏ添加は耐粒界腐食改善に有効であり、Ｗ添加は析出硬化に有効であるという理由による。これらを単独添加又は複合添加することができる。また、それを０．０１〜５．０重量％の範囲とするのは０．０１重量％未満であると添加効果がなく、５．０重量％を超えると脆化し、また抵抗値の温度係数が大きくなってしまうという問題があるので、上限を５．０重量％とする。 Regarding B, the reason of 0.001 to 1.5% by weight is that if it is less than 0.001% by weight, the effect of addition for obtaining a fine crystal grain structure is small even in the cast structure and the forged structure. This is because if it exceeds wt%, it becomes brittle due to precipitation of a boron compound or the like. The reason for N being 0.001 to 1.5% by weight is that if less than 0.001% by weight, the effect of addition for obtaining sufficient workability is small, and if it exceeds 1.5% by weight, nitrides This is because the material is embrittled by precipitation. Further, the addition of Be, Mg and Si is effective for strengthening the material, the addition of Ti is effective for preventing intergranular corrosion, the addition of V is effective for improving wear resistance, and the addition of Co or Ni is a γ phase. This is because the addition of Cu or Nb is effective for improving the corrosion resistance, the addition of Mo is effective for improving the intergranular corrosion resistance, and the addition of W is effective for precipitation hardening. These can be added alone or in combination. Moreover, if it is less than 0.01% by weight, the effect is not added if it is in the range of 0.01 to 5.0% by weight, and if it exceeds 5.0% by weight, it becomes brittle and the temperature coefficient of resistance Therefore, the upper limit is set to 5.0% by weight.
本発明の鉄合金は、比抵抗値を１５０μΩ・ｃｍ以上にさせることができ、また±２００ｐｐｍ／℃の範囲内の温度係数を有し、耐熱、耐食性に優れた材料が得られるという効果を有する。 The iron alloy of the present invention can have a specific resistance value of 150 μΩ · cm or more, has a temperature coefficient within a range of ± 200 ppm / ° C., and has an effect that a material excellent in heat resistance and corrosion resistance can be obtained. .
本発明合金の製造方法としては、まずＭｎ：１０．０〜４５．０重量％、Ａｌ：５．０〜１５．０重量％、Ｃ：０．０１〜２．０重量％、Ｃｒ：０．０１〜１５．０重量％、残部Ｆｅからなる組成範囲内で成分調整する。また、必要に応じて、Ｂ：０．００１〜１．５重量％、Ｎ：０．００１〜１．５重量％、Ｂｅ、Ｍｇ、Ｓｉ、Ｔｉ、Ｖ、Ｃｏ、Ｎｉ、Ｃｕ、Ｎｂ、Ｍｏ、Ｗ：それぞれ０．０１〜５．０重量％、から選択した元素の１種又は２種以上を所定量添加して、適宜原料成分を調整する。 As the method for producing the alloy of the present invention, Mn: 10.0 to 45.0% by weight, Al: 5.0 to 15.0% by weight, C: 0.01 to 2.0% by weight, Cr: 0.00. The components are adjusted within the composition range of 01 to 15.0% by weight and the balance Fe. Further, as necessary, B: 0.001 to 1.5% by weight, N: 0.001 to 1.5% by weight, Be, Mg, Si, Ti, V, Co, Ni, Cu, Nb, Mo , W: A predetermined amount of one or two or more elements selected from 0.01 to 5.0% by weight are added, and the raw material components are appropriately adjusted.
次に、これをアーク溶解炉又は高周波溶解炉を用いて溶解し、これを鋳造インゴットとし、さらに８００℃〜１３００℃の温度にて熱間鍛造あるいは熱間圧延及び２００℃〜１１００℃までの温度にて焼鈍を行いながら冷間圧延・伸線等の加工工程を経て、また必要に応じて、２００℃〜１３００℃の温度にて熱処理後、焼き入れ又は空冷して製造する。その後、さらに必要に応じて、２００℃〜７００℃の温度にて時効熱処理して製造する。以上のようにして作製された材料の結晶組織は、γ相（ｆｃｃ構造）、α相（ｂｃｃ構造）、Ｃｒ炭化物などから形成される。 Next, this is melted using an arc melting furnace or a high-frequency melting furnace, which is used as a casting ingot, and further hot forging or hot rolling at a temperature of 800 ° C. to 1300 ° C. and a temperature of 200 ° C. to 1100 ° C. It is manufactured through a heat treatment at a temperature of 200 ° C. to 1300 ° C., followed by quenching or air cooling, if necessary, through processing steps such as cold rolling and wire drawing while annealing. Thereafter, it is further manufactured by aging heat treatment at a temperature of 200 ° C. to 700 ° C. as necessary. The crystal structure of the material produced as described above is formed of γ phase (fcc structure), α phase (bcc structure), Cr carbide, and the like.
次に実施例および比較例により本発明をさらに詳細に説明する。本発明の鉄合金の範囲で、実施例１〜実施例３２を表１、表２及び表３に示した。実施例１−実施例３２の組成の合金について、高周波溶解炉を用いて溶解し、これを鋳造インゴットとした。次に１１００℃の温度にて、熱間圧延、１１００℃あるいは１２００℃の温度にて１５分の熱処理、及び水中焼き入れあるいは空冷の製造工程、またその後、必要に応じて３００℃〜５００℃の時効熱処理を経て鉄合金を作製した。 Next, the present invention will be described in more detail with reference to examples and comparative examples. In the range of the iron alloy of the present invention, Examples 1 to 32 are shown in Tables 1, 2 and 3. Example 1 An alloy having the composition of Example 32 was melted using a high-frequency melting furnace to obtain a cast ingot. Next, at a temperature of 1100 ° C., hot rolling, heat treatment for 15 minutes at a temperature of 1100 ° C. or 1200 ° C., and a manufacturing process of quenching in water or air cooling, and then 300 ° C. to 500 ° C. as necessary An iron alloy was prepared through aging heat treatment.
同様に、比較例１−比較例１３を表１に示した。比較例１−比較例１３の組成の合金について、高周波溶解炉を用いて溶解し、これを鋳造インゴットとした。次に１１００℃の温度にて、熱間圧延、１１００℃あるいは１２００℃の温度にて１５分の熱処理、及び水中焼き入れあるいは空冷の製造工程を経て鉄合金を作製した。 Similarly, Comparative Example 1 to Comparative Example 13 are shown in Table 1. Comparative Example 1—The alloy having the composition of Comparative Example 13 was melted using a high-frequency melting furnace, and this was used as a casting ingot. Next, an iron alloy was manufactured through a manufacturing process of hot rolling at a temperature of 1100 ° C., heat treatment for 15 minutes at a temperature of 1100 ° C. or 1200 ° C., and quenching in water or air cooling.
また、表１に、本発明の実施例１−実施例２５の鉄合金および比較例１−比較例１３の鉄合金の、熱処理条件、存在する相、冷間圧延率（％）、比抵抗値（μΩ・ｃｍ）、抵抗値の温度係数（ｐｐｍ／℃）（２０℃〜１００℃における）を示した。 Table 1 shows heat treatment conditions, existing phase, cold rolling rate (%), specific resistance value of the iron alloy of Example 1 to Example 25 and the iron alloy of Comparative Example 1 to Comparative Example 13 of the present invention. (ΜΩ · cm), temperature coefficient of resistance (ppm / ° C.) (at 20 ° C. to 100 ° C.).
【表１】
表１に示たし通り、実施例１−実施例２５の合金は、冷間圧延率６０％という優れた加工性および１５０μΩ・ｃｍ以上の高い比抵抗値および±２００ｐｐｍ／℃内の小さい温度係数を有する。これに対し、比較例１−比較例１３については、優れた加工性を有するが、比抵抗値が低く、温度係数も±２００ｐｐｍ／℃を超えている。あるいは、比抵抗値が充分に高く温度係数が小さくても、加工性が非常に悪くなっている（冷間圧延率２０％以下）。 As shown in Table 1, the alloys of Examples 1 to 25 have excellent workability of a cold rolling rate of 60%, a high specific resistance value of 150 μΩ · cm or more, and a small temperature coefficient within ± 200 ppm / ° C. Have On the other hand, Comparative Example 1 to Comparative Example 13 have excellent workability, but have a low specific resistance value and a temperature coefficient exceeding ± 200 ppm / ° C. Alternatively, even if the specific resistance value is sufficiently high and the temperature coefficient is small, the workability is very poor (cold rolling rate of 20% or less).
表２は、実施例１５および実施例１８の鉄合金において、比抵抗値および温度係数に及ぼす時効熱処理の影響を調査した結果を示している。表２に示すとおり、適切な時効熱処理を施し、γ相、α相およびＣｒ炭化物の量を制御することにより、特に、抵抗値の温度係数を小さくすることができることがわかる。 Table 2 shows the results of investigating the influence of aging heat treatment on the specific resistance value and the temperature coefficient in the iron alloys of Example 15 and Example 18. As shown in Table 2, it can be seen that the temperature coefficient of the resistance value can be particularly reduced by performing an appropriate aging heat treatment and controlling the amounts of the γ phase, α phase and Cr carbide.
表３は、実施例１３および実施例３１の鉄合金の耐熱性を調査した結果を示している。本発明の合金の耐熱性は、１５０℃にて２週間保持することにより調査した。表に示すとおり、本発明の合金は、１５０℃にて２週間保持してもその比抵抗値、温度係数は殆ど変化せず、耐熱性、経時変化にも極めて優れていることがわかる。 Table 3 shows the results of investigating the heat resistance of the iron alloys of Example 13 and Example 31. The heat resistance of the alloys of the present invention was investigated by holding at 150 ° C. for 2 weeks. As shown in the table, it can be seen that the specific resistance value and temperature coefficient of the alloy of the present invention hardly change even when held at 150 ° C. for 2 weeks, and are extremely excellent in heat resistance and change with time.
本発明の鉄合金は、加工性に優れ、比抵抗値が高く、温度特性にも優れ、さらに耐熱性、耐食性に富む材料を低コストで得られるという効果を有する。従って、高抵抗器用材料、一般パワー抵抗器、精密抵抗器、電熱線などに使用することができる。本発明は、前記の実施例によってなんら限定されるものではない。すなわち、本発明の技術思想の範囲における他の例、態様等を当然含むものである。
The iron alloy of the present invention has an effect that a material having excellent workability, high specific resistance, excellent temperature characteristics, and excellent heat resistance and corrosion resistance can be obtained at low cost. Therefore, it can be used for materials for high resistors, general power resistors, precision resistors, heating wires, and the like. The present invention is not limited to the above-described embodiments. That is, other examples, aspects, and the like within the scope of the technical idea of the present invention are naturally included.
Claims (6)
添加元素として、さらにＢ：０．００１〜１．５質量％、Ｎ：０．００１〜１．５質量％、Ｂｅ、Ｍｇ、Ｓｉ、Ｔｉ、Ｖ、Ｃｏ、Ｎｉ、Ｃｕ、Ｎｂ、Ｍｏ及びＷ：それぞれ０．０１〜５．０質量％、からなる群から選択した１種又は２種以上の元素を含有することを特徴とする高抵抗器用鉄合金。 Mn: 10.0-45.0% by mass , Al: 5.0-15.0% by mass , C: 0.0. In an iron alloy for high resistors, characterized by comprising 5 to 2.0 mass %, Cr: 0.01 to 15.0 mass %, the balance Fe and inevitable impurities ,
As additional elements, B: 0.001 to 1.5 mass%, N: 0.001 to 1.5 mass%, Be, Mg, Si, Ti, V, Co, Ni, Cu, Nb, Mo, and W : An iron alloy for high resistors, comprising one or more elements selected from the group consisting of 0.01 to 5.0% by mass, respectively.
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